A twelve‐analyzer detector system for high‐resolution powder diffraction

A dedicated high‐resolution high‐throughput X‐ray powder diffraction beamline has been constructed at the Advanced Photon Source (APS). In order to achieve the goals of both high resolution and high throughput in a powder instrument, a multi‐analyzer detector system is required. The design and performance of the 12‐analyzer detector system installed on the powder diffractometer at the 11‐BM beamline of APS are presented.     

A curved image‐plate detector system for high‐resolution synchrotron X‐ray diffraction

The developed curved image plate (CIP) is a one‐dimensional detector which simultaneously records high‐resolution X‐ray diffraction (XRD) patterns over a 38.7° 2θ range. In addition, an on‐site reader enables rapid extraction, transfer and storage of X‐ray intensity information in ≤30 s, and further qualifies this detector to study kinetic processes in materials science. The CIP detector can detect and store X‐ray intensity information linearly proportional to the incident photon flux over a dynamical range of about five orders of magnitude. The linearity and uniformity of the CIP detector response is not compromised in the unsaturated regions of the image plate, regardless of saturation in another region. The speed of XRD data acquisition together with excellent resolution afforded by the CIP detector is unique and opens up wide possibilities in materials research accessible through X‐ray diffraction. This article presents details of the basic features, operation and performance of the CIP detector along with some examples of applications, including high‐temperature XRD.     

基于高光谱技术检测全蛋粉掺假的研究

传统食品掺假分析多集中于检测特定已知或者怀疑可能存在的掺假物,然而由于掺假形式的多样性以及新的掺假物不断出现,使得传统检测方法具有局限性。目前,全蛋粉作为鲜蛋理想替代品掺假现象十分严重,然而不管是国内还是国外,其掺假检测都鲜有研究。因此,为了探索一种快速检测全蛋粉掺假的方法,研究尝试使用最近快速发展起来的具有绿色、无损等优点的高光谱技术来检测全蛋粉掺假的可行性。从不同地区收集不同品牌的鸡蛋全蛋粉,按不同比例分别掺入淀粉、大豆分离蛋白、麦芽糊精以及三种掺假物的混合物进行试验样品的制备。样品进行光谱采集后,采用ENVI软件选取感兴趣区域(ROI)后提取出平均光谱。根据获得的光谱数据建立全波段下支持向量机(SVM)模型进行掺假的判别并采用偏最小二乘回归(PLSR)模型建立全波段与掺假浓度之间的关系。结果显示,采用径向基核函数所建立的SVM模型,其分类的正确率达到90%以上,基于PLSR建立掺假模型实际值与预测值相关系数R2_P均高于0.90。为了简化模型,采用回归系数法(RC)及连续投影法(SPA)提取特征波长,根据特征波长下的光谱数据建立RC-PLSR和SPA-PLSR模型,结果显示,经简化的模型依然具有良好的性能,说明使用高光谱技术来检测全蛋粉掺假是可行且高效的。     

A New Scheme for High‐Intensity Laser‐Driven Electron Acceleration in a Plasma

We propose a new approach to high‐intensity relativistic laser‐driven electron acceleration in a plasma. Here, we demonstrate that a plasma wave generated by a stimulated forward‐scattering of an incident laser pulse can be in the longest acceleration phase with injected relativistic beam electrons. This is why the plasma wave has the maximum amplification coefficient which is determined by the acceleration time and the breakdown (overturn) electric field in which the acceleration of the injected beam electrons occurs. We must note that for the longest acceleration phase the relativity of the injected beam electrons plays a crucial role in our scheme. We estimate qualitatively the acceleration parameters of relativistic electrons in the field of a plasma wave generated at the stimulated forward‐scattering of a high‐intensity laser pulse in a plasma. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Use of N‐chloro‐N‐methyl‐p‐toluenesulfonamide in N‐chlorination reactions

Second‐order rate constants (k₂) were determined for the addition of ten nitrogenous organic compounds (benzylamine, 2,2,2‐trifluoethylamine chlorhidrate, methylamine chlorhidrate, glycine ethyl ester chlorhidrate, glycine, glycylglycine chlorhidrate, morpholine, pyperidine, pyperazine and dimethylamine) to the N‐chloro‐N‐methyl‐p‐toluenesulfonamide (NCNMPT) in the formation reaction of N‐chloramines in aqueous solution at 25 °C and ionic strength 0.5 M. The series of nucleophiles considered is structurally very varied and covers five pK_a units. The kinetic behaviour is similar for all compounds, being the elementary step the transfer of chlorine from the NCNMPT molecule to the nitrogen of the free amino group. These reactions were found first order in both reagents. The values of the rate constants indicate that the more basic amines produce N‐chloramines more readily. Rate constants for the nucleophilic attack are shown to correlate with literature data for some of these nitrogenous organic compounds in their reaction with N‐methyl‐N‐nitroso‐p‐toluenesulfonamide. Both reactions involve that the rate determining step is the attack of nitrogenous compounds upon electrophilic centre (Cl or else NO group). NCNMPT is a particularly interesting substrate, for which has not hitherto been published kinetic information, that allows us to assess the efficiency and the competitiveness of this reaction and compare it with other agents with a Cl⁺ atom. Copyright © 2013 John Wiley & Sons, Ltd.     

Nano‐in‐Micro POxylated Polyurea Dendrimers and Chitosan Dry Powder Formulations for Pulmonary Delivery

Pulmonary administration offers excellent advantages over conventional drug delivery routes, including increasing therapeutics bioavailability, and avoiding long‐term safety issues. Formulations of nano‐in‐micro dry powders for lung delivery are engineered using (S)‐ibuprofen as a model drug. These biodegradable formulations comprise nanoparticles of drug‐loaded POxylated polyurea dendrimers coated with chitosan using supercritical‐fluid‐assisted spray drying. The formulations are characterized in terms of morphology, particle‐size distribution, in vitro aerodynamic particle pulmonary distribution, and glutathione‐S‐transferase assay. It is demonstrated that ibuprofen‐loaded nanoparticles can be successfully incorporated into microspheres with adequate aerodynamic properties, mass median aerodynamic diameter (1.86–3.83 μm), and fine particle fraction (28%–45%), for deposition into the deep lung. The (S)‐ibuprofen dry powder formulations show enhanced solubility, high swelling behavior and a sustained drug release at physiologic pH. Also, POxylated polyureas decrease the (S)‐ibuprofen toxic effect on cancer cellular growth. The 3‐(4,5‐dimethylthiazol‐2‐yl)‐5‐(3‐carboxymethoxyphenyl)‐2‐(4‐sulfophenyl)‐2H‐tetrazolium (MTS) assays show no significant cytotoxicity on the metabolic activity of human lung adenocarcinoma ephithelial (A549) cell line for the lowest concentration (1 × 10^?3 m ), even for longer periods of contact with the cells (up to 120 h), and in the normal human dermal fibroblasts cell line the toxic effect is also reduced.     

Fabrication and testing of a newly designed slit system for depth‐resolved X‐ray diffraction measurements

A new system of slits called `spiderweb slits' have been developed for depth‐resolved powder or polycrystalline X‐ray diffraction measurements. The slits act on diffracted X‐rays to select a particular gauge volume of sample, while absorbing diffracted X‐rays from outside of this volume. Although the slit geometry is to some extent similar to that of previously developed conical slits or spiral slits, this new design has advantages over the previous ones in use for complex heterogeneous materials and in situ and operando diffraction measurements. For example, the slits can measure a majority of any diffraction cone for any polycrystalline material, over a continuous range of diffraction angles, and work for X‐ray energies of tens to hundreds of kiloelectronvolts. The design is generated and optimized using ray‐tracing simulations, and fabricated through laser micromachining. The first prototype was successfully tested at the X17A beamline at the National Synchrotron Light Source, and shows similar performance to simulations, demonstrating gauge volume selection for standard powders, for all diffraction peaks over angles of 2–10°. A similar, but improved, design will be implemented at the X‐ray Powder Diffraction beamline at the National Synchrotron Light Source II.     

Large‐aperture prism‐array lens for high‐energy X‐ray focusing

A new prism‐array lens for high‐energy X‐ray focusing has been constructed using an array of different prisms obtained from different parabolic structures by removal of passive parts of material leading to a multiple of 2π phase variation. Under the thin‐lens approximation the phase changes caused by this lens for a plane wave are exactly the same as those caused by a parabolic lens without any additional corrections when they have the same focal length, which will provide good focusing; at the same time, the total transmission and effective aperture of this lens are both larger than those of a compound kinoform lens with the same focal length, geometrical aperture and feature size. This geometry can have a large aperture that is not limited by the feature size of the lens. Prototype nickel lenses with an aperture of 1.77 mm and focal length of 3 m were fabricated by LIGA technology, and were tested using CCD camera and knife‐edge scan method at the X‐ray Imaging and Biomedical Application Beamline BL13W1 at Shanghai Synchrotron Radiation Facility, and provided a focal width of 7.7 µm and a photon flux gain of 14 at an X‐ray energy of 50 keV.     

X‐ray nanotomography and focused‐ion‐beam sectioning for quantitative three‐dimensional analysis of nanocomposites

Knowing the relationship between three‐dimensional structure and properties is paramount for complete understanding of material behavior. In this work, the internal nanostructure of micrometer‐size (～10 µm) composite Ni/Al particles was analyzed using two different approaches. The first technique, synchrotron‐based X‐ray nanotomography, is a nondestructive method that can attain resolutions of tens of nanometers. The second is a destructive technique with sub‐nanometer resolution utilizing scanning electron microscopy combined with an ion beam and `slice and view' analysis, where the sample is repeatedly milled and imaged. The obtained results suggest that both techniques allow for an accurate characterization of the larger‐scale structures, while differences exist in the characterization of the smallest features. Using the Monte Carlo method, the effective resolution of the X‐ray nanotomography technique was determined to be ～48 nm, while focused‐ion‐beam sectioning with `slice and view' analysis was ～5 nm.     

A novel multi‐detection technique for three‐dimensional reciprocal‐space mapping in grazing‐incidence X‐ray diffraction

A new scattering technique in grazing‐incidence X‐ray diffraction geometry is described which enables three‐dimensional mapping of reciprocal space by a single rocking scan of the sample. This is achieved by using a two‐dimensional detector. The new set‐up is discussed in terms of angular resolution and dynamic range of scattered intensity. As an example the diffuse scattering from a strained multilayer of self‐assembled (In,Ga)As quantum dots grown on GaAs substrate is presented.     

Design and development of a controlled pressure/temperature set‐up for in situ studies of solid–gas processes and reactions in a synchrotron X‐ray powder diffraction station

A novel set‐up has been designed and used for synchrotron radiation X‐ray high‐resolution powder diffraction (SR‐HRPD) in transmission geometry (spinning capillary) for in situ solid–gas reactions and processes in an isobaric and isothermal environment. The pressure and temperature of the sample are controlled from 10^?3 to 1000 mbar and from 80 to 1000 K, respectively. To test the capacities of this novel experimental set‐up, structure deformation in the porous material zeolitic imidazole framework (ZIF‐8) by gas adsorption at cryogenic temperature has been studied under isothermal and isobaric conditions. Direct structure deformations by the adsorption of Ar and N₂ gases have been observed in situ, demonstrating that this set‐up is perfectly suitable for direct structural analysis under in operando conditions. The presented results prove the feasibility of this novel experimental station for the characterization in real time of solid–gas reactions and other solid–gas processes by SR‐HRPD.     

基于便携式拉曼高光谱成像技术的散装奶粉中硫脲可视化现场快速检测方法研究

硫脲是一种含氮量高、毒性较大的潜在蛋白掺假化合物,常规的实验室检测方法过程复杂、效率低,无法满足口岸对大批次散装奶粉样本质量快速筛查的需求。为解决口岸抽样监管缺乏快速实时评价方法的难题,利用自主搭建的便携式点扫描拉曼高光谱成像系统,开发了一种简单高效的奶粉中硫脲现场可视化快速检测方法,确保散装奶粉在进出口环节的精准监管。研究以不同添加浓度（0.005%~2.000%）的硫脲奶粉混合物为样本,分别用Whittaker平滑方法和自适应迭代重加权惩罚最小二乘算法（airPLS）消除光谱数据的背景随机噪音信号和荧光背景干扰,峰值识别后对硫脲特征位移处的单波段数据进行二值化处理,得到混合样本感兴趣区域的二值热图,通过二值图中硫脲像素点的有无和坐标,对奶粉中的硫脲进行定性判别和定位分析。进一步分析得感兴趣区域内硫脲像素点数目与添加浓度的关系,结果表明随着添加浓度的增加,硫脲像素点数目呈线性增长趋势,其中线性拟合的决定系数(R2)为0.991 3,硫脲的最低检出浓度为0.05%。在0.25%,0.60%,1.20%和1.50%的添加水平下,利用像素点数目和线性拟合关系预测奶粉中硫脲的浓度,结果显示预测浓度的相对误差范围为-9.41%~4.01%,相对标准偏差小于7%。该点扫描拉曼高光谱成像系统能在10 min内完成单个样本的检测,结合软件控制系统,实时对奶粉中的硫脲颗粒进行定性、定量和污染分布分析,方法简单高效、准确性好、灵敏度高、稳定性强,为口岸现场对散装奶粉中硫脲掺假物的实时快速检测提供了技术监管手段,能显著提升口岸现场散装样本的监管环节质量评价的精准性,为进口奶粉快速通关提供技术保障。     

New hierarchy for the Liouville equation,irreversibility and Fokker‐Planck‐like structures

The issue of irreversibility is revisited for a closed system formed by N classical non‐relativistic particles inside a volume Ω, interacting through two‐body potentials, for large N and Ω. The classical phase‐space distribution function f, multiplied by suitable Hermite polynomials and integrated over all momenta, yields new moments. The Liouville equation and the initial distribution f_in imply a new non‐equilibrium linear infinite hierarchy for the moments. That hierarchy differs from the BBGKY one for distribution functions and displays some suggestive Fokker‐Planck‐like structures. A physically motivated ansatz for f_in (which introduces statistical assumptions), used by previous authors, is chosen. All moments of order n ≥ n₀ are expressed in terms of those of order n₀ — 1 and of f_in. The properties of the Fokker‐Planck‐like structures (hermiticity, non‐negative eigenvalues) allow for implementing a natural long‐time approximation in the hierarchy, so as to introduce relaxation to equilibrium and irreversibility, consistently with the hydrodynamical balance equations. Further (more restrictive) assumptions and approximations lead to new irreversible models, generalizing non‐trivially the Fokker‐Planck equation. They are described through a truncated hierarchy of linear equations for moments of order n ≤ n₀ — 1 (n₀ being finite). The connections with Brownian particle dynamics and Fluid Dynamics are analyzed, for consistency.     

A facile method for flexible GaN‐based light‐emitting diodes

Flexible GaN‐based light‐emitting diodes (LEDs) on polyethylene terephthalate (PET) substrates are demonstrated. The process uses commercial LEDs on patterned sapphire substrates, laser lift‐off (LLO), wet etching for additional surface roughening, and mounting of the freestanding LED on a PET substrate. Electrical and optical properties from the free‐standing LLO‐LEDs mounted on the flexible PET substrates were characterized. The process is scalable to large wafer diameters. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A fast energy‐dispersive multi‐element detector for X‐ray absorption spectroscopy

In this paper results are presented from fluorescence‐yield X‐ray absorption fine‐structure spectroscopy measurements with a new seven‐cell silicon drift detector (SDD) module. The complete module, including an integrated circuit for the detector readout, was developed and realised at DESY utilizing a monolithic seven‐cell SDD. The new detector module is optimized for applications like XAFS which require an energy resolution of ～250–300 eV (FWHM Mn Kα) at high count rates. Measurements during the commissioning phase proved the excellent performance for this type of application.     

A 3‐state defect model for light‐induced degradation in boron‐doped float‐zone silicon

We report on a light‐induced bulk defect activation and subsequent deactivation in boron doped float‐zone silicon that can be described by a 3‐state model. During treatment at elevated temperature and illumination, a sample first converts from an initial high lifetime state into a degraded low lifetime state and then shows a recovery reaction leading to a third high lifetime state that is then stable under degradation conditions. Furthermore, it is shown that reverse reactions into the initial state appear to be possible both from the degraded as well as the regenerated state. An injection dependent analysis of lifetime data yields a defect capture cross section ratio of ～20 suggesting a positively charged defect. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Catalysis by hydrogen chloride in the gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐buten‐3‐ol

A homogeneous, molecular, gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐ buten‐3‐ol catalyzed by hydrogen chloride in the temperature range 325–386 °C and pressure range 34–149 torr are described. The rate coefficients are given by the following Arrhenius equations: for 2‐phenyl‐2‐propanol log k₁ (s^?1) = (11.01 ± 0.31) ? (109.5 ± 2.8) kJ mol^?1 (2.303 RT)^?1 and for 3‐methyl‐1‐buten‐3‐ol log k₁ (s^?1) = (11.50 ± 0.18) ? (116.5 ± 1.4) kJ mol^?1 (2.303 RT)^?1. Electron delocalization of the CH₂?CH and C₆H₅ appears to be an important effect in the rate enhancement of acid catalyzed tertiary alcohols in the gas phase. A concerted six‐member cyclic transition state type of mechanism appears to be, as described before, a rational interpretation for the dehydration process of these substrates. Copyright © 2007 John Wiley & Sons, Ltd.